Recent Advances in Nickel Catalyzed Carbonylative Reactions via the Insertion of Carbon Monoxide†

Comprehensive Summary Carbonyl compounds have attracted considerable attention due to their extensive applications in drug discovery. Furthermore, they are important synthetic intermediates for the construction of carbon‐carbon and carbon‐heteroatom bonds. Transition‐metal‐catalyzed carbonylation via the insertion of CO is one of the most efficient and straightforward strategies to access carbonyl compounds. However, most of the transition‐metal‐catalyzed carbonylative reactions require expensive and toxic noble‐metal catalysts. Therefore, there is a growing demand for the exploration of nickel‐catalyzed carbonylative reactions via the insertion of CO due to the earth abundance and low cost of nickel. Compared with the well‐established palladium‐catalyzed carbonylative reactions, nickel‐catalyzed analogous transformations have been relatively underdeveloped. This is primarily because CO strongly binds to nickel, often resulting in catalyst poisoning. In recent years, some research groups have focused on using CO surrogates or NN 2 pincer nickel catalyst to circumvent the formation of Ni(CO) 4 . Nickel‐catalyzed carbonylation has been applied in the construction of carbonyl‐containing compounds, such as ketones, carboxylic acids, thioesters, acyl chloride and carboxamides.